US5482769A - Cross-linked film - Google Patents

Cross-linked film Download PDF

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Publication number
US5482769A
US5482769A US08/252,300 US25230094A US5482769A US 5482769 A US5482769 A US 5482769A US 25230094 A US25230094 A US 25230094A US 5482769 A US5482769 A US 5482769A
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United States
Prior art keywords
film
cross
blend
copolymer
polyolefin
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Expired - Lifetime
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US08/252,300
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English (en)
Inventor
Henry G. Schirmer
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Cryovac LLC
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WR Grace and Co Conn
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Priority to US08/252,300 priority Critical patent/US5482769A/en
Assigned to W.R. GRACE & CO.-CONN. reassignment W.R. GRACE & CO.-CONN. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHIRMER, HENRY G.
Priority to BR9502616A priority patent/BR9502616A/pt
Priority to EP95303795A priority patent/EP0685523B1/de
Priority to DE69530725T priority patent/DE69530725T2/de
Priority to AT95303795T priority patent/ATE240367T1/de
Application granted granted Critical
Publication of US5482769A publication Critical patent/US5482769A/en
Assigned to CRYOVAC, INC. reassignment CRYOVAC, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: W.R. GRACE & CO.-CONN.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y10T428/31917—Next to polyene polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention pertains to compositions for making packaging film, and more particularly to a thin polymeric film suitable for replacing polyvinyl chloride film especially in packaging applications.
  • PVC Polyvinyl chloride
  • PVC has several desirable properties for this use. For example, it has excellent burn-through resistance, optics and good elasticity and stretch properties at use temperatures.
  • PVC also has several disadvantages, including the production of hydrogen chloride gas during heat sealing and the generally corrosive effects of such gases in the packaging room. Extractables from the PVC into the packaged food product have also become of concern.
  • U.S. Patent No. 3,456,044 mentions thin films of thicknesses less than 1 mil such as 0.5 mils, and discloses a double bubble method for biaxially orienting thermoplastic films, including the steps of producing a primary tubing which is inflated by introducing air into the interior thereof, and a cooling ring 22, as well as squeeze rolls 34 and 28, with rolls 34 having a greater speed than rolls 28. Between the two pairs of squeeze rolls is a reinflated secondary bubble. If annealing is desired, the tubing can be reinflated to form a bubble 70.
  • U.S. Pat. No. 4,258,166 discloses a uniaxially oriented plastic film material with improved strength and clarity in the direction of orientation preferably comprising homopolymers and copolymers of ethylene.
  • U.S. Pat. No. 4,355,076 discloses monoaxially oriented polypropylene film laminated to a monoaxially oriented high density polyethylene film, the films produced by for example tubular blowing.
  • U.S. Pat. No. 4,440,824 discloses a thermoformable coextruded multilayer structure useful for thermoforming into containers, the structure having polyolefin coextruded with a high impact polystyrene layer. A five layer structure is shown.
  • U.S. Pat. No. 4,464,439 discloses a coextruded laminate having a sheet of polypropylene and a sheet of a mixture of high impact polystyrene, crystalline polypropylene, and styrene/dienic monomer block copolymer.
  • U.S. Pat. No. 4,879,177 (Boice) discloses a monoaxially oriented shrink film having a core layer of butadiene styrene copolymer, outer layers of ethylene propylene copolymer, and intermediate bonding layers of ethylene copolymer.
  • thermoplastic film useful as an overwrap material for trayed retail cuts of meat and other food products in a supermarket or other retail environments.
  • the inventor has discovered that a blend of a polyolefin, a diene polymer and a transition metal catalyst cross-links in the presence of oxygen. This provides a film with heat resistance, especially burn-through resistance.
  • the film of the present invention is a cross-linked, stretch-oriented film with heat resistance and good optical properties.
  • the film can desirably be provided as a laminate with an outer sealable layer and preferably with an intermediate adhesive layer.
  • the final laminate may have a thickness of from 0.5-5 mils, and desirably may be used as a thin laminate in thicknesses from 0.5-2 mils.
  • the cross-linked, stretch-oriented film of the present invention offers considerable advantages. It is cross-linked linked without irradiation and obtains high heat resistance. Further, it is stretch-oriented to achieve desirable properties and may readily be formed into an advantageous laminate.
  • the polyolefin is preferably VLDPE (very low density polyethylene) or LLDPE (linear, low density polyethylene), although others can readily be used, as polypropylene and copolymers of ethylene and propylene. Homogeneous ethylene alpha olefin copolymers can also be used in connection with this invention.
  • the diene polymer blended with the polyolefin provides unsaturated groups.
  • Typical diene polymers include octadienes, hexadienes, 1,4-polybutadiene, 1,2-polybutadiene, non-conjugated dienes and heptadienes.
  • the transition metal catalyst is in the form of a salt, with the metal thereof selected from the first, second or third transition series of the Periodic Table.
  • Suitable metals include, but are not limited to, manganese II or III, iron II or III, cobalt II or III, nickel II or III, copper I or II, rhodium II, III or IV, and ruthenium.
  • the oxidation state of the metal when introduced is not necessarily that of the active form.
  • the metal is preferably iron, nickel or copper, more preferably manganese and most preferably cobalt.
  • Suitable counterions for the metal include, but are not limited to, chloride, acetate, stearate, palmitate, 2-ethylhexanoate, neodecanoate or naphthenate.
  • Particularly preferable salts include cobalt (II) 2-ethylhexanoate and cobalt (II) neodecanoate.
  • the metal salt may also be an ionomer, in which case a polymeric counterion is employed. Such ionomers are well known in the art.
  • the blend is preferably stretch oriented before cross-linking.
  • the blend is coextruded through a die in the conventional manner and the extruded film hot blown to form a blown bubble.
  • an air cooling ring may be positioned circumferentially around the blown bubble to cool same as it exits the die.
  • the blown bubble is melt oriented in both the machine and transverse directions using various blow up ratios, but preferably the bubble is hot blown to a blow-up ratio of between 1.5 and 8. If desired, one may immediately reinflate the bubble after cooling into a secondary bubble and then expand same to impart orientation of the material in primarily the transverse direction, primarily the longitudinal direction, or in both the transverse and longitudinal directions.
  • the bubble is collapsed in a set of pinch rolls and transferred to a take-up roll.
  • This procedure is shown, for example, in U.S. Pat. No. 5,219,666, which is incorporated herein by reference in its entirety.
  • alternate methods may be utilized for providing the stretch oriented film.
  • outer layers 12 as shown in FIG. 1 may comprise a polyolefin or desirably an ethylene polymer or copolymer such as ethylene vinyl acetate copolymer (EVA).
  • EVA ethylene vinyl acetate copolymer
  • One may also desirably use styrenic polymers and copolymers, for example, styrene butadiene copolymer, such as that commercially available from Phillips under the designation KR-10 having a butadiene content of 25% by weight of the copolymer, or KK-36 (for fatty food contact).
  • styrene butadiene copolymers are used for the outer layers, especially block copolymers containing a major portion (greater than 50%) of styrene and a minor portion (less than 50%) of butadiene comonomer. These materials provide an optimum balance of stiffness and flexibility to the film.
  • Core layer 10 preferably comprises the blend of the present invention, i.e. a blend of a polyolefin and a diene polymer, and a transition metal catalyst. More than one polyolefin can be used in the blend, as well as more than one diene polymer.
  • polymer includes herein not only homopolymers, but copolymers and terpolymers as well provided they blend with the other components to provide a cross-linkable blend.
  • the outer layers 12 are bonded to the core layer 10 by means of intermediate layers 14 comprising, for example, a polymeric adhesive and preferably a copolymer of ethylene, and more preferably an ethylene vinyl acetate copolymer (EVA).
  • intermediate layers 14 comprising, for example, a polymeric adhesive and preferably a copolymer of ethylene, and more preferably an ethylene vinyl acetate copolymer (EVA).
  • EVA ethylene vinyl acetate copolymer
  • Other polymeric materials, including chemically modified adhesives, can be used for layers 14 provided that they process adequately in processes such as those discussed herein. Blends of polymeric materials and polymeric adhesives may also be used for intermediate layers.
  • anti-fog/plasticizing agents such as Atmer 645 (a trademark of ICI), a proprietary antifog/plasticizer and/or Atmer 1010 (a trademark of ICI), a glycerol ester liquid are preferably included, desirably in amounts between about 0.5 and 10% by weight of the layer or layers.
  • the intermediate layers 14 of the present invention also desirably may contain such agents in the aforesaid amounts.
  • the multi-layer film of the present invention is preferably prepared by coextrusion techniques as discussed hereinabove.
  • SBC is a styrene butadiene copolymer available from Phillips under the designation KK36-2.
  • the SBC materials of the skin layers included about 2% each, by weight of the layer, of ATMER 1010 (a trademark of ICI), a glycerol ester liquid and ATMER 645 (a trade mark of ICI), a proprietary antifog/plasticizer; both Atmer materials are used as antifog agents, and are available from ICI.
  • EVA is an ethylene vinyl acetate copolymer, and in the examples produced in accordance with the invention, the EVA actually comprised a blend of 50% (by weight) of an EVA resin, and 50% (by weight) of an EVA master batch.
  • the EVA resin was Elvax 3165 available from DuPont. This resin has a vinyl acetate content of about 18% by weight.
  • the EVA master batch comprised 92%, by weight of the master batch, of Elvax 3165, and 4% each, by weight of the master batch, of ATMER 1010 (a trademark of ICI), a glycerol ester liquid and ATMER 645 (a trademark of ICI), a roprietary antifog/plasticizer.
  • the BLEND 1 of Example 1 was made up of:
  • VLDPE (DEFD 1015-8 available from Union Carbide) which has a density of about 0.900 and a melt index of about 0.1;
  • an LLDPE master batch i.e. a blend of 40% by weight of a linear low density polyethylene, and 30% each, by weight, of ATMER 1010 and ATMER 645 (a trademark of ICI), a proprietary antifog/plasticizer, the LLDPE master batch provided commercially under the designation Santec 23-222.
  • the BLEND 2 of Example 2 was like BLEND 1, but also included 5%, by weight of the blend, of cobalt decanoate master batch, wherein a cobalt decanoate material was compounded with EVA resin.
  • EVA (9% VA) comprises 97.7% of the master batch,and the cobalt decanoate comprised 2.3% of the master batch.
  • the core layer 10 of Example 3 contained very low density polyethylene, the DEFD 1015 material available from Union Carbide.
  • the cross-linkable material of the invention is very useful in producing a heat resistant material useful in overwrap applications such as those described above.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US08/252,300 1994-06-01 1994-06-01 Cross-linked film Expired - Lifetime US5482769A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US08/252,300 US5482769A (en) 1994-06-01 1994-06-01 Cross-linked film
BR9502616A BR9502616A (pt) 1994-06-01 1995-05-31 Filme reticulável e filme orientado reticulável
EP95303795A EP0685523B1 (de) 1994-06-01 1995-06-01 Verfahren zum Verpacken von Nahrungsmitteln
DE69530725T DE69530725T2 (de) 1994-06-01 1995-06-01 Verfahren zum Verpacken von Nahrungsmitteln
AT95303795T ATE240367T1 (de) 1994-06-01 1995-06-01 Verfahren zum verpacken von nahrungsmitteln

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/252,300 US5482769A (en) 1994-06-01 1994-06-01 Cross-linked film

Publications (1)

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US5482769A true US5482769A (en) 1996-01-09

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Application Number Title Priority Date Filing Date
US08/252,300 Expired - Lifetime US5482769A (en) 1994-06-01 1994-06-01 Cross-linked film

Country Status (5)

Country Link
US (1) US5482769A (de)
EP (1) EP0685523B1 (de)
AT (1) ATE240367T1 (de)
BR (1) BR9502616A (de)
DE (1) DE69530725T2 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100411740B1 (ko) * 2001-08-28 2003-12-18 금호타이어 주식회사 금속과 고무간의 접착력을 강화한 고무조성물
US20060003093A1 (en) * 2003-03-04 2006-01-05 Pactiv Corpoation Antifogging compositions and methods for using same
US20100272975A1 (en) * 2009-04-23 2010-10-28 Chevron Phillips Chemical Company Lp System and method for the production and use of lamination films
US9517611B2 (en) 2010-02-26 2016-12-13 Coveris Flexibles Us Llc Multi-layer low temperature shrink film
US11273627B2 (en) 2017-01-11 2022-03-15 Bostik, Inc. Extrudable antifog copolyester heat seal resins

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1346824B1 (de) * 1996-03-29 2009-05-13 Cryovac, Inc. Zusammensetzungen und Verfahren zur selektiven Vernetzung von Filmen, sowie die damit hergestellten Filmartikel
US5993922A (en) * 1996-03-29 1999-11-30 Cryovac, Inc. Compositions and methods for selectively crosslinking films and improved film articles resulting therefrom
IL120622A (en) * 1996-04-09 2000-02-17 Raytheon Co System and method for multimodal interactive speech and language training
JP5019248B2 (ja) 2004-11-24 2012-09-05 東洋製罐株式会社 酸素吸収性樹脂組成物
WO2006065651A2 (en) 2004-12-17 2006-06-22 Dow Global Technologies Inc. Rheology modified polyethylene compositions

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3456044A (en) * 1965-03-12 1969-07-15 Heinz Erich Pahlke Biaxial orientation
US3555604A (en) * 1965-03-12 1971-01-19 Union Carbide Corp Biaxial orientation
US4258166A (en) * 1979-06-08 1981-03-24 Mobil Oil Corporation Low density polyethylene film
US4355076A (en) * 1976-08-04 1982-10-19 Koninklijke Emballage Industrie Van Leer, B.V. Dry lamination
US4440824A (en) * 1981-10-23 1984-04-03 Composite Container Corporation Thermoformable coextruded multilayered structure
US4461792A (en) * 1982-09-30 1984-07-24 Union Carbide Corporation Poly-1-butene multilayers plastic film
US4464439A (en) * 1981-03-12 1984-08-07 Montefina S.A. Co-extruded laminate consisting of at least one sheet of polypropylene and at least one sheet of polymeric material based on high-impact polystyrene
US4879177A (en) * 1987-11-13 1989-11-07 W. R. Grace & Co. Monoaxially oriented shrink film
EP0507207A2 (de) * 1991-04-02 1992-10-07 W.R. Grace & Co.-Conn. Zusammensetzungen, Gegenstände und Methode zur Entfernung von Sauerstoff
US5211875A (en) * 1991-06-27 1993-05-18 W. R. Grace & Co.-Conn. Methods and compositions for oxygen scavenging
US5219666A (en) * 1990-03-23 1993-06-15 W.R. Grace & Co.-Conn. Oriented film of high clarity and gloss

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0546546A1 (de) * 1991-12-11 1993-06-16 Toppan Printing Co., Ltd. Harzzusammensetzung mit beschränkter Sauerstoffdurchlässigkeit und Verfahren zu deren Herstellung
US5399289A (en) * 1992-10-01 1995-03-21 W. R. Grace & Co.-Conn. Compositions, articles and methods for scavenging oxygen which have improved physical properties

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3456044A (en) * 1965-03-12 1969-07-15 Heinz Erich Pahlke Biaxial orientation
US3555604A (en) * 1965-03-12 1971-01-19 Union Carbide Corp Biaxial orientation
US4355076A (en) * 1976-08-04 1982-10-19 Koninklijke Emballage Industrie Van Leer, B.V. Dry lamination
US4258166A (en) * 1979-06-08 1981-03-24 Mobil Oil Corporation Low density polyethylene film
US4464439A (en) * 1981-03-12 1984-08-07 Montefina S.A. Co-extruded laminate consisting of at least one sheet of polypropylene and at least one sheet of polymeric material based on high-impact polystyrene
US4440824A (en) * 1981-10-23 1984-04-03 Composite Container Corporation Thermoformable coextruded multilayered structure
US4461792A (en) * 1982-09-30 1984-07-24 Union Carbide Corporation Poly-1-butene multilayers plastic film
US4879177A (en) * 1987-11-13 1989-11-07 W. R. Grace & Co. Monoaxially oriented shrink film
US5219666A (en) * 1990-03-23 1993-06-15 W.R. Grace & Co.-Conn. Oriented film of high clarity and gloss
EP0507207A2 (de) * 1991-04-02 1992-10-07 W.R. Grace & Co.-Conn. Zusammensetzungen, Gegenstände und Methode zur Entfernung von Sauerstoff
US5211875A (en) * 1991-06-27 1993-05-18 W. R. Grace & Co.-Conn. Methods and compositions for oxygen scavenging

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100411740B1 (ko) * 2001-08-28 2003-12-18 금호타이어 주식회사 금속과 고무간의 접착력을 강화한 고무조성물
US20060003093A1 (en) * 2003-03-04 2006-01-05 Pactiv Corpoation Antifogging compositions and methods for using same
US7794794B2 (en) * 2003-03-04 2010-09-14 Pactiv Corporation Antifogging compositions and methods for using same
US20100272975A1 (en) * 2009-04-23 2010-10-28 Chevron Phillips Chemical Company Lp System and method for the production and use of lamination films
US9517611B2 (en) 2010-02-26 2016-12-13 Coveris Flexibles Us Llc Multi-layer low temperature shrink film
US11273627B2 (en) 2017-01-11 2022-03-15 Bostik, Inc. Extrudable antifog copolyester heat seal resins
US11806971B2 (en) 2017-01-11 2023-11-07 Bostik, Inc. Extrudable antifog copolyester heat seal resins
US12570079B2 (en) 2017-01-11 2026-03-10 Bostik, Inc. Extrudable antifog copolyester heat seal resins

Also Published As

Publication number Publication date
BR9502616A (pt) 1996-04-30
EP0685523B1 (de) 2003-05-14
ATE240367T1 (de) 2003-05-15
EP0685523A1 (de) 1995-12-06
DE69530725D1 (de) 2003-06-18
DE69530725T2 (de) 2004-03-25

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